Dialdehyde as diketone-cyclic amide condensation products



United States Patent Ofiice 3,431,271 Patented Mar. 4, 1969 3,431,271 DIALDEHYDE AS DIKETONE-CYCLIC AMIDE CONDENSATION PRODUCTS William Julius van Loo, Jr., Middlesex, N.J., assignor to American Cyanamid Company, Stamford, Conn., a

corporation of Maine No Drawing. Filed May 26, 1965, Ser. No. 459,093

US. Cl. 260-307 5 Claims Int. Cl. C07d 91/24, 85/26, 27/00 ABSTRACT OF THE DISCLOSURE As finishing agents capable of imparting crease resistance to cellulosic textiles without increasing their chlorine retention, condensation products of a dialdehyde or diketone with two mols of a cyclic amide of the structure where A is oxygen, sulfur or alkylene and R is hydrogen or alkyl.

This invention relates to novel textile finishing agents, to a method for finishing and particularly for imparting crease resistance to textile materials by the use of these novel agents and to the textile materials finished and crease proofed therewith.

A major objective of the textile industry is the development and use of new finishing agents, particularly for wash and wear fabrics, in order to achieve various additive effects such as improvement of wrinkle resistance and dimensional stability and to impart crease proofing properties to such materials. More specifically, it is desired to impart such properties to cellulose-containing textile materials which are blends of cotton and synthetic fibers. As employed herein, by the term finishing or like term is meant the imparting of (or if a finishing agent the ability to impart) these additive effects, as well as other qualities to be described hereinafter, to such textile materials.

While various textile finishing resins alone or in combination with other resins and/ or agents have been em ployed for many years in the art of textile finishing, many such combinations show marked deficiencies in some respects. Thus, treating resins such as the aminoplast resins (reaction products of nitrogen compounds with aldehydes, ketones, acetals or ketals) have proved beneficial due to their ability to crosslink the cellulose fiber chains. The crosslinking is conventionally achieved by treating the textile material with the finishing agent in an acidic bath followed by a curing operation such as conventional pressing and heating. Of the aminoplast resins the reaction products of amines or amides such as urea, thiourea, ethyleneurea, melamines, guanamines and the like with formaldehyde have held particular interest because of the ease of formation of crosslinking functional groups in the finishing agent.

However, the use of finishing agents prepared with formaldehyde have serious drawbacks. Thus, many of these resinous materials contain free formaldehyde which gives rise to an obnoxious odor during preparation, storage, usage in textile finishing and in the subsequent storage of finished goods particularly under humid conditions. This requires costly and space-consuming ventilation systems and special efforts during fabric treatment such as use of buffers or process washing to alleviate the odor. In addition to the odor problems created by the presence of free formaldehyde, the dermatitic effect of free formaldehyde is also a well-known problem.

Another problem with such resins arises when textile materials finished with the resins undergo cleaning operations in which chlorine or chlorine-containing compounds are added for purposes of bleaching and the like. Subsequent to the cleaning and washing procedure it is common to dry or press the fabrics as with a heated iron. A common harmful result of these operations is the liberation of some of the chlorine retained in the fabric in a manner so as to cause a degradative effect on the tensile strength of the fabric. It will be evident moreover that the propensity of a finishing agent to retain chlorine, which chlorine may be liberated during subsequent heating or pressing operations, will cause later discoloration of the fabric and give rise to the objectionable odor of chloramides when washed in the presence of chlorine bleaching agents.

In US. application Ser. No. 86,865, filed Feb. 3, 1961, now US. Patent 3,185,539, in which one of the present applicants is coinventor, there is disclosed a process for treating cellulose textile material which comprises applying thereto a compound of the formula:

where R and R are alkyl or alkenyl having from 1 to about 20 carbon atoms, R and R are: hydrogen, alkyl having from 1 to 20 carbon atoms inclusive, or phenyl, R and R are hydrogen or lower alkyl and n is an integer of from 0 to 8 inclusive.

Among the essential differences of the foregoing process and treating compound is the absence in the novel finishing compound of the present invention of a hydrogen atom attached to the nitrogen atom of the amide portion of the molecule as will be evident from the structure shown hereinafter. Although the finishing compounds of the cited patent application are highly beneficial, the presence of the hydrogen atom on the nitrogen tends to promote retention of chlorine in the molecule during conventional washing and bleaching operations of fabric finished with the compound. As already mentioned the presence of retained chlorine gives rise to damage of the fabric during heating or pressing operations. In the compounds of the present invention, however, the nitrogen atom is blocked by certain substituents thereby preventing chlorine retention and consequent damage to the fabric.

Aminoplast resins are normally manufactured as aqueous solutions, usually of from between 40 to 70% solids. This requires the shipment of substantial amounts of water, frequently over substantial distances. Obviously, it would be advantageous to ship the resins as solids or as concentrated solutions.

Additionally, the aminoplast resins of the prior art can, in some instances, cause significant damage to direct dyes on cellulosic fabrics which normally is the result of the presence of free formaldehyde in the resinous products. A finishing resin which avoids these and other problems would therefore provide substantial benefits to the textile finishing industry.

It is therefore an object of the invention to provide a class of finishing agents particularly for imparting wrinkle resistance and durable creases and designs tocellulose containing textile materials.

It is a further object of the invention to provide a class of textile finishing agents which do not retain the chlorine usually employed in bleaching and washing cellulose containing textile materials, thereby avoiding the subsequent discoloration, the chloramide odor and the strength loss commonly observed after heating or pressing such materials.

A further object of the invention is to provide a class of textile finishing agents which do not contain formaldehyde or other substances possessing obnoxious odors and irritating fumes which are liberated during treating, drying, curing, crease-setting and like operations.

Another object of the invention is to provide a novel class of textile finishing agents which may be purified to crystalline solids and mobile liquids and can therefore be easily transported, thus minimizing or reducing the cost of transporting these agents.

Other objects of the invention include providing a process for finishing cellulose containing textile material particularly to obtain crease proofing through application of the class of compounds of the invention and the provision of cellulose containing textile materials finished with said novel compounds.

These and other objects, advantages and features of the invention "will become more apparent from the detailed description hereinafter.

Accordingly, the present invention encompasses novel compounds of the general formula wherein A is selected from the group consisting of oxygen, sulfur and lgl LRJ... R is selected from the group consisting of hydrogen and alkyl, particularly lower alkyl containing from 1 to 7 carbon atoms inclusive; R is selected from the group consisting of hydrogen, alkyl containing from 1 to about 20 carbon atoms inclusive, hydroxy and alkoxy, particularly lower alkoxy containing from 1 to 7 carbon atoms inclusive; R is selected from the group consisting of hydrogen, alkyl containing from 1 to about 20 carbon atoms inclusive and phenyl; n is an integer of from to 8 inclusive; and m is an integer of from 1 to 3 inclusive.

It 'will be seen from Formula I that the compounds of the invention have a combined cyclic and linear structure wherein the functional groups (hydroxy, alkoxy) capable of crosslinking cellulose are in the linear portion of the molecule, and the unreactive portions are in the cyclic amide portion of the molecule. It will be further noted from Formula I that no hydrogen atoms are attached to the nitrogen atoms. This is significant as explained above in that the nitrogen atoms are blocked with inert substituents thereby preventing the retention of chlorine and consequent chlorine damage to fabrics treated with the finishing agents.

Preferred lower alkyl substituents are groups containing from 1 to 7 carbon atoms. Any of the alkyl or lower alkyl groups may be normal or branch chained. As examples of such lower alkyl radicals there may be mentioned methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, hexyl, heptyl and the like. Illustrative of the alkyl radicals not limited to lower alkyl groups are octyl, nonyl, decyl, tridecyl, pentadecyl, and up to and including eicosyl (C Lower alkoxy includes groups containing from 1 to 7 carbon atoms inclusive such as methoxy, ethoxy, butoxy and the like, including normal and branch chain isomers. When A is 51. LR |m typical groupings are the straight chains CH C H and C H and Such groups having alkyl side chains, e.g.,

etc.

Particularly preferred compounds falling within the general Formula I are those wherein R" on the carbon atom alpha to the amide nitrogen atom is hydrogen, that is, compounds of the structural formula:

wherein A, R, R, R", n and m are as already defined above. It is believed that compounds of the above structural formula tend to be more water soluble than other members of the class of compounds of the invention although the other compounds encompassed by Formula I would be operable when applied to textile fabric in aqueous emulsions containing suitable surface active agents. Illustrative compounds of Formula II are N,N- (1,2-dihydroxyethylene bis (2-pyrrolidone), N,N'-(1,2-dihydroxyethylene)bis(2-oxazolidone) and N,N-(1,2-dimethoxyethylene) bis Z-pyrrolidone).

The compounds of the invention are prepared by reacting a cyclic amide with a suitable dialdehyde, diketone, mixed aldehyde-ketone acetal or mixed acetal-ketal. The typical compound structure of the cyclic amides is as follows:

(III) wherein A and R are as defined above.

Illustrative cyclic amides include the following subgeneric classes of compounds and representative members.

(1) 2-pyrrolidones:

Z-pyrrolidone 3-methyl-2-pyrrolidone 3,4-dimethyl-Z-pyrrolidone 4-ethyl-2-pyrrolidone 3-propyl-2-pyrrolidone, etc. 2-oxazolidones:

2-oxazolidone 4-methyl-2-oxazolidone 4,4-dimethyl-Z-oxazolidone 4-ethyl-2-oxazolidone 4-propyl-2-oxazolidone, etc.

Z-thiazolidones:

4-methyl-2-thiazolidone 4,5-dimethyl-2-thiazolidone 4-ethyl-2-thiazolidone 4-propyl-2-thiazolidone, etc.

(4) Z-piperidones:

Z-piperidone 3-methyl-2-piperidone 3,S-dimethyl-Z-piperidone 3-ethyl-2-piperidone 3-propyl-2-piperidone, etc.

(5 Tetrahydro-ZH-1,3-oxazin-2-ones:

tetrahydro-ZH-l,3-oxazin-2-one 4-methyltetrahydro-2H-1,3-0xazin-2-one 5,S-dimethyltetrahydro-ZH-1,3-oxazin-2-one 4-ethyltetrahydro-2H-1,3-oxazin-2-one S-propyltetrahydro-ZH-l,3-oxazin-2-one, etc.

(6) Tetrahydro-ZH-1,3-thiazin-2-ones tetrahydro-ZH-1,3-thiazin-2-one 4-methyltetrahydro-2H-1,3-thiazin-2-one G-methyltetrahydro-ZH- l ,3-thiazin-2-one 4,4-dimethyltetrahydro-2H-1,3-thiazin-2-one, etc. (7) Hexahydro-ZH-azepin-Z-ones:

hexahydro-ZH-azepin-Z-one 3-methylhexahydro-2H-azepin-2-one 3,3-dimethylhexahydro-2H-azepin-Z-one 3,4-dimethylhexahydro-ZH-azepin-2-one 4,5-dimethylhexahydro-2Hazepin-2-one, etc. (8) Hexahydro-1,3-oxazepin-2-ones:

hexahydro-l,3-oxazepin-2-one 4-methylhexahydro-1,3-oxazepin-2-one -6,6-dimethylhexahydro-1,3-oxazepin-2-one 4,7-dimethylhexahydro-1,3-oxazepin-2-one 4-ethylhexahydro-1,3-oxazepin-2-one, etc. (9) Hexahydro-1,3-thiazepin-2-ones:

hexahydro-1,3-thiazepin-2-one 4-methylhexahydro-1,3-thiaZepin-2-one 7,7-dimethylhexahydro-l,3-thiazepin-2-one 5,7-dimethylhexahydrol-1,3 -thiazepin-2-one 4-ethylhexahydro-1,3-thiazepin-2-one, etc.

The dialdehydes, diketones, substituted dialdehydes and mixed aldehyde-ketones have the structure:

Fl" it -C-O-R Lit .n (IV) and the acetals, ketals and mixed acetal-ketals have the structure:

CH-CHC RO LIL. in OR (V) (1) Dialdehydes: glyoxal malonaldehyde succinaldehyde glutaraldehyde adipaldehyde pimelaldehyde suberaldehyde azelaaldehyde sebacaldehyde, etc.

(2) Substituted dialdehydes:

Z-methylmalonaldehyde Z-butylmalonaidehyde 2-methylsuccinaldehyde 2,B-dimethylglutaraldehyde 2-methyladipaldehyde, etc.

(3) Diketones:

2,3butadione 2,3-pentadione 3-methyl-2,4-pentadione 3-pheny1-2,4-pentadione 2,4-heptadione, etc.

(4) .Mixed aldehyde-ketones:

2-oxopropionaldehyde 2-oxobutyraldehyde 3-methyl-2-oxobutyraldehyde 4-phenyl-3-oxobutyraldehyde Z-oxohexanal, etc.

(5 Acetals:

1, 1,3,3-tetramethoxypropane 1,1,3,3-tetraethoxypropane The reaction between the cyclic amide of Formula III and one or more coreactants of Formulas IV and V is carried out in an aqueous or alcoholic medium under essentially neutral pH conditions, e.g., pH 6-10 and more preferably pH 78, and at a temperature effective to cause reaction, e.g., in the range of 30 C. to C. Preferably the reaction is conducted under reflux conditions. The time of reaction is not critical and will be inversely proportional to the temperature employed. Generally from about one minute to several hours will be suitable and at higher temperatures from about 2 to 10 minutes will be effective. Excessively high temperatures should be avoided since polymerization may occur. Excessively low temperatures, e.g., 0 C. or less, are not useful since the reaction would be too slow for economy.

Products wherein an alkoxy group is attached to the carbon atom alpha to the nitrogen atom of the cyclic amide terminal groups may also be prepared by reacting a dialdehyde, diketone, or mixed aldehyde-ketone, i.e., reactants of Formula IV, with the cyclic amide and an alcohol at a pH of less than about 4.0 in an aqueous medium. The alcohol is one or a mixture of two or more of the structure ROH wherein R is as defined above. In effect, the alcohol serves to alkylate the aldehyde or ketone to form the corresponding acetal or ketal of Formula V which in turn reacts with the cyclic amide. For complete alkylation at least 2 moles of alcohol should be employed per mole of Formula IV compound. Preferably substantial excess of alcohol will be employed since it may function as a solvent for the reaction. Suitable alcohols are methanol, ethanol, propanol, butanol and the like. Sufficient acid or acid generating material should be present in the reaction mixture to maintain the acidity at the required pH. The common acids are useful for this purpose, including mineral acids, e.g., sulfuric, hydrochloric, nitric, phosphoric, and the like; organic acids, e.g., oxalic, propionic, maleic, paratoluene, sulfonic, and the like; and acid salts, e.g., monosodium-dihydrogenphosphate, monoammonium dihydrogenphosphate, and the like. Reaction temperature is not critical and broadly may range from about 0 C. to 100 C. Preferred temperature is room temperature (20 C.30 C.). Reaction time is inversely proportional to the temperature and may be of the same duration as described above.

Alternatively to the latter procedure, the procedure described in U.S. Patent 3,091,617 may be followed.

The cyclic amides and compounds of Formulas IV or V in any of the above reactions are normally reacted in stoichiometric amounts, i.e., at least about 2 moles of cyclic amide per mole of coreactant. However, slight excesses of either reactant may be employed. The reaction may be carried out at atmospheric pressure, subatmospheric pressure or superatmospheric pressure and the process may be batch, semicontinuous or continuous. Water is the usual reaction medium although other solvents may be employed with water, preferably such inert polar solvents as pyridine, quinoline, dioxane and the like.

By the term cellulose textile material, as that term and similar terms are employed herein, is meant fibers,

yarns, filaments, formed fabrics, whether woven or nonwoven, felted or otherwise formed, containing at least 50% of cellulose fiber prepared from cotton, rayon, linen, flax and other cellulosic materials. These cellulosic materials may be employed in combination with other noncellulosic materials. For example, they may be blended with other natural or synthetic fibers, e.g., wool, nylon, acrylic fibers, polyester fibers and the like. The compounds or textile finishing agents of this invention may be applied to cellulosic textile materials by any conventional technique, such as immersion, padding, spraying and the like, followed where necessary by squeezing, hydroextraction or similar processes in order to afiix the desired amount of solids on the fabric.

The method of application should be such that from about 1 to about 25% and in some instances higher amounts of the product of this invention based on the weight of the fabric are deposited thereon. Within certain limits, the amount of agent applied depends upon the particular type of fabric being treated. Thus, when treating fabric consisting of fibrous cellulosic materials, the concentration of the order of about 1 to 25% and more particularly from 3 to solids, based on the dry weight of the fabric, may be employed.

The catalyst or accelerator employed to promote cure of the finishing agent on the textile material is applied after the finishing agent or simultaneously therewith. The accelerator is an acidic type catalyst and may be a free acid, acid salt, alkanolamine salt, metal salt and the like of the type well known to those in the textile finishing art. The concentration of catalyst employed may range from about 0.1 to about or higher, based on the weight of the solids, depending upon the particular catalyst type employed. Thus, for example, from between about 0.1% and about 10% of a free acid such as phosphoric, tartaric, oxalic or the like may be employed, while in the case of ammonium chloride amounts of from between 0.5 and about 10% are used. In the case of amine salts including alkanolamine salts, such as diethanolamine hydrochloride, from about 1 to about 10% are most useful, while with respect to salts such as magnesium chloride amounts of from between about 5 and 25% have been successfully employed. In addition to magnesium chloride, zinc nitrate, aluminum chloride and other known metal salts are normally employed in amounts corresponding to between 5 and 25% based on the weight of the solids.

Following the application of the finishing agent and curing catalyst to the textile fabric, the material is subjected to drying and curing operations in order to achieve wrinkle resistance and shrinkage control. The drying and curing operation may be carried out in a single step or in separate steps. The temperatures at which the drying and curing operations are effected may vary widely and are influenced to some extend by the type of catalyst employed. Normally, the range of temperature extends from about 180 F. to about 450 F. or even higher. Generally speaking, the time of the drying and/ or curing operation is inversely proportional to the temperature employed and of course is influenced by whether or not separate or combined drying and curing steps are employed. Generally, when drying and curing is carried out in a combined operation, a time of from about one minute to about 10 minutes may be employed at temperatures from 450 to 250 F., respectively. When the fabric has been dried preliminary to curing, curing times of the order of 5 minutes to about A minute at a temperature of from between 250 to 450 F., respectively, have been successfully employed.

In order that the present invention may be more completely understood, the following examples are given in which all parts are parts by weight unless otherwise specified. These examples are set forth primarily for the purpose of illustration and any specific enumeration of detail contained therein should not be interpreted as a limitation on the case except where indicated in the appended claims.

Example 1.N,N-(1,Z-dihydroxyethylene)bis(2- To a suitable vessel was charged 170 grams of 2- pyrrolidone of essentially purity, 85.3 grams of glyoxal of 68% purity (32% water), and 200 grams of methanol. After stirring this mixture for several minutes, 4 pellets of NaOH (95% purity) were added. Heat was applied to bring the mixture to reflux during which period solution was elfected. Refluxing was continued for one hour and then cooling was effected. A crystalline product was obtained which was purified by recrystallization from methanol. Elemental analyses were in excellent agreement with theoretical values. The crystals had a melting point of 192-196 C. and represented a yield of 54%.

Example 2.N,N-( 1,2-dihydroxyethylene bis 2- oxazolidone) II I OH OH O O/ N(i,HHN \O Hz (1H2 H20 CH2 Example 1 was followed substantially except that 174 grams of 2-oxazolidone were substituted for the 2- pyrrolidone employed in Example 1. The recrystallized product gas excellent agreement of elemental analyses with theoretical values.

Example 3 .N,N'- 1,Z-dimethoxyethylene)bis(2- pyrrolidone) Example 4 Application baths were prepared of the products of Examples 1, 2, and 3 by dissolving 15 grams of each compound in about cc. of water with moderate heating. After cooling to room temperature 18 cc. of a 10% aqueous solution of magnesium chloride were added and final volume was adjusted to 200 cc. Two yards of 80 x 80 count cotton pereale of 16 inch width were then treated with said baths employing a Microset padder and obtaining a wet pickup of 80%, based on the dry weight of fabric. The treated fabrics were dried for 2 minutes at 225 F. and then cured for 1.5 minutes at 350 F. Wrinkle recovery values of the treated fabrics were as follows:

9 The wrinkle recovery test was Tentative Test Method 66-1959T as described in the Manual of the American Association of Textile Chemists and Colorists (AATCC).

Example The compounds of the invention produce no significant tensile strength loss due to chlorine retention as compared to losses of about 100% and 50% produced by dimethylol urea and methylolated ethylene urea, respectively, each of which contains nitrogen atoms having hydro-gen substituents rendering the same susceptible to chlorine retention.

Example 6 Cotton percale was treated in accordance with Example 4 except that the curing operation was omitted. A portion of each fabric was submitted to a crease-setting operation employing a Hoflfman Garment Press operating at 280 F. with no cover cloth on the top plate. The treating cycle was steam for 30 seconds, press dry for 30 seconds and evacuate for 10 seconds. This cycle was run first on one side of a switch 11 x 13 inches folded in half so as to form a crease and then repeated on the other side. After crease-setting, the swatches were cured in an oven for 15 minutes at 325 F. During the creasesetting and subsequent curing operations, no objectionable fumes or odors were detected. After 25 washings in a Kenmore washer with intervening line-dryings, all treated fabrics showed excellent crease retention and wash-wear appearance.

Example 7 Example 1 was repeated except that the following weights of ingredients were employed:

Grams Glyoxal 68% purity (1.0 mole) 85.5 2-pyrrolidone (1.12 moles) 190.0 Methanol 793 =NaOH (95% purity) -1 After refluxing for 1 hour and cooling, 28.5 grams of crystalline product of melting point 194196 C. was obtained. Partial evaporation of methanol yielded an additional 106 grams of crystalline product of melting point 186-192 C. Recrystallization of the product gave a product of melting point 194-196 C. A yield of 5 3 resulted.

Analysis.Theory: C, 52.6; H, 7.01; N, 12.28. Found: C, 52.64, 52.68; H, 7.30, 7.17; N, 11.87, 12.10.

This reaction shows that even with variations in the mole ratio of reactants essentially the same product is obtained as in Example 1.

Example 8 The compound of Example 3 was applied to cotton percale with two different catalyst concentrations as follows. The pH of each pad bath was 7.4.

10 (A) Pad bath (set A fabric): Grams Compound (61%) 36.9 Magnesium chloride (10% aqueous) 27.0 Ethanol 50.0 Water to total 300 cc. (B) Pad bath (set B fabric):

Compound (61%) 36.9 Magnesium chloride (10% aqueous) 13.5 Ethanol 50.0

Water to total 300 cc.

A total of three yards of fabric of sixteen inch width was padded through each bath (A and B) using a Micro set padder and obtaining a wet pickup of The treated fabric was dried 2 minutes at 225 F. Two yards of each set of the treated fabric were then cured 1.5 minutes at 350 F. while the third yard of each set was held for crease-setting and post-cure studies. The crease-setting and post-curing were performed as described in Example 6.

All of the treated fabrics contained 6% of reactant solids based on the weight of fabric. Set A contained 12% solids (based on reactant present) of magnesium chloride as catalyst while the set B contained 6% magnesium chloride on the same basis. The results of various physical property determinations made on the treated fabrics are given below. The test procedures are those as indicated in Examples 4, 5 and 6 unless otherwise specified.

1 The wrinkle recovery test was Tentative Test Method 66-19591 as described in the Manual of the American Association of Textile Chemists and Colorists (AATCC).

Sours: 0.02% NazSiFn for 5 minutes at F. After five such sours the fabrics were rinsed in water and then subjected to the American Association of Textile Chemists and Colorists Chlorine Retention Test 92-1962 except that scorching was for 30 seconds at 365 F.

3 American Association of Textile Chemists and Colorists Tentative Test Method 88C-1964T.

4 Wash and wear appearance ratings: American Association of Textile Chemists and Colorists Tentative Test Method 8811-19641.

This example shows that good wrinkle recovery improvement, crease retention, and wash-wear appearance are obtained with the compounds of this invention at either acid catalyst level with no chlorine damage.

The textile finishing agents of this invention may be employed alone or in combination with other crease proofing resins and in particular with other aminoplast textile finishing resins, as for example, melamine-formaldehyde resins, guanamine-formaldehyde resins, and their alkylated or etherified derivatives. Thus, for example, the agents of this invention may be combined with the melamine-formaldehyde resins which are described in U.S. Patent No. 2,197,357 and U.S. Patent No. 2,529,856. Additionally, they may be combined with various cyclic ureas, as for example, ethylene urea, propylene urea, including the 1,2- and 1,3-propylene ureas and their homologues and corresponding thio derivatives and the thiobis amides such as are described in U.S. Patent No. 2,887,408. Suitable guanamine-formaldehyde condensates of the type contemplated for use with the agents of this invention are those described in U.S. PatentNo. 2,887,409. Additionally, the agents of this invention may be combined or employed with urons such as are described in U.S. Patent No. 2,375; and various polyepoxide resins having epoxy equivalents greater than '1, as for example those described in U.S. Patent No. 2,730,427, U.S. Patent No. 2,752,269 and U.S. Patent No. 2,794,754. Further, the textile finishing agents of this invention may be employed with other agents or auxiliaries, as for example, softeners, lubricants, odorants and the like.

wherein A is selected from the group consisting of oxygen, sulfur and l l Lid...

R is selected from the group consisting of hydrogen and alkyl of 1-7 carbon atoms;

R is selected from the group consisting of hydrogen, alkyl of 12() carbon atoms, hydroxy and alkoxy of 1-7 carbon atoms;

R" is selected from the group consisting of hydrogen,

alkyl of 1-20 carbon atoms and phenyl;

n is an integer of from to 8 inclusive, and

m is an integer of from 1 to 3 inclusive.

12 wherein A is selected from the group consisting of oxygen, sulfur and Lgl LRJ...

References Cited Agfa Chem. Abst., vol. 56, columns 6827-8 (1961).

Oda et al.: Chem. Abst., vol. 57, columns 13748-9 (1962).

Vail et al.: Jour. Org. Chem, vol. 30, pages 1195-9 (1965, April).

HENRY R. JILES, Primary Examiner.

NATALIE TROUSOF, Assistant Examiner.

US. Cl. X.R. 

